Method for cleaning and/or deodorizing toilet bowl or urinal using an adhesive agent

ABSTRACT

Method for cleaning and/or deodorizing a toilet bowl or urinal. In one embodiment, the method involves directly applying an agent to the toilet bowl or urinal. The agent adheres to the toilet bowl or urinal and can be flushed away only after a relatively large number of flushing operations. The agent includes fillers from the group of surfactants and also an adhesion promoter. The viscosity of the agent is at least 30 Pas, measured using a Haake viscometer, plate/plate system, plate diameter 10 mm, at a shear gradient of 2.62 s −1  and 20° C. and the agent is so sticky that it can serve to attach bar-shaped agents to the toilet bowl or urinal, wherein the concentration of the surfactants in the case of an adhesion promoter from the group of polvalkyleneimines is between 7 and 60% by weight. The agent may have associated with it one or more bar-shaped compositions.

The present application is a continuation-in-part of U.S. patentapplication Ser. No. 12/735,987, inventors Joachim Leipold et al., filedAug. 30, 2010, which in turn is a 371 of PCT Application No.PCT/EP2009/000873, filed Feb. 9, 2009, both of which are incorporatedherein by reference.

The present invention relates to an adhesive agent for the sanitarysector, which serves in particular for application on a sanitary objectsuch as a toilet bowl.

These agents are viscous, generally pasty agents, which are applieddirectly to the surface of the sanitary object from a suitablecontainer, adhere there and can be flushed away only after a relativelylarge number of flushing operations.

WO 99/66017 discloses adhesive sanitary agents which serve for cleaningand deodorization and comprise surfactants, water, fragrances andadhesion promoters. Following direct application on the sanitary object,these sanitary agents are flushed away only after a relatively largenumber of flush cycles.

A further development of these adhesive sanitary agents with smoothersurfaces as a consequence of additions of polyhydric alcohols isdisclosed in EP 1 325 103 B1.

Further adhesive sanitary agents based on block copolymers comprisingoligo- or polyalkylene oxides or on aryl ethoxylates or alkyl arylethoxylates as adhesion promoters are described in EP 1 318 191 B1 andadhesive sanitary agents containing bleaches are described in DE 10 2004056 554 A1.

The known adhesive sanitary agents can be applied in a simple andhygienic manner using a suitable device, they adhere to the surface ofthe sanitary object, retain their shape and are not flushed away intheir entirety even under the effect of water, but only graduallydissolve completely after a large number of flushes.

The particular advantage of these adhesive sanitary agents consists inthe fact that additional containers such as the so-called “WC cages”,the use of which is perceived by the consumer as being unhygienic,particularly when replacing the sanitary agent and when cleaning thetoilet, are avoided.

In the field of conventional bar-shaped toilet cleaning anddeodorization agents which are used in WC cages in the toilet bowl, inrecent years a large number of multiphase products has been supplied:

Thus, for example, agents with an additional bleach phase are describedin WO 00/23558, agents with a cleaning agent shaped-body phase and a gelphase are described in EP 1 418 225 A1 and cleaning agent shaped bodieswith one phase comprising water-soluble salts and one phase comprisingwater-insoluble salts are described in WO 00/58434.

As a result of dividing the various functions to be fulfilled by atoilet cleaning and deodorization agent between several phases, forexample a specific phase for intense deodorization and a special phaseexclusively for cleaning, such multiphase agents are able to better meetthe requirements of the consumer.

The object of the present invention is to provide a sanitary agent whichcan be applied in a simple and hygienic manner, which can be used indiverse ways and which fulfils consumer wishes with regard to intensedeodorization and good cleaning.

This object is achieved by an agent for the sanitary sector, which agentcan be applied directly on the sanitary object, adheres there and can beflushed away only after a relatively large number of flushingoperations, where the agent comprises fillers from the group ofsurfactants and also an adhesion promoter, characterized in that theadhesion promoter is selected from the group of polyalkylene derivativeswhich comprise polyalkylene chains with randomly distributed functionalgroups, or from the group of copolymers from the group ofmonoalkylesters of poly/methyl vinylethers/carboxylic anhydrides, olefinhomopolymers and copolymers of two or more olefins being partiallyoxidized or further functionalized via graft molecules, and from thegroup of polyalkyleneimines, also in alkoxylated form, polyether amines(alkoxylated amines) and polyglycerol polyether alkylcarboxylic acids orpolymers or derivatives containing these polymer groups and theviscosity of the agent is at least 30 Pas, measured using a Haakeviscometer, plate/plate system, plate diameter 10 mm, at a sheargradient of 2.62 s⁻¹ and 20° C. and the agent is so sticky that it canserve to attach bar-shaped agents in the toilet bowl, wherein theconcentration of the surfactants in the case of an adhesion promoterfrom the group of polyalkyleneimines is between 7 and 60% by weight.

Surprisingly, it has been established that an agent with a viscosity ofat least 30 Pas, measured using a Haake viscometer, plate/plate system,plate diameter 10 mm, at a shear gradient of 2.62 s⁻¹ and 20° C., whichcomprises fillers and also an adhesion promoter, where the adhesionpromoter is selected from the group of polyalkylene derivatives,silicone systems, copolymers from the group of monoalkyl esters ofpoly(methyl vinyl ethers/carboxylic anhydrides, olefin homopolymers andcopolymers of two or more olefins, being partially oxidized or furtherfunctionalized via graft molecules, and polyalkyleneimines, also inalkoxylated form, polyether amines (alkoxylated amines) and polyglycerolpolyether alkylcarboxylic acids (esters of alkoxylated polyglycerols) orpolymers or derivatives of these compounds containing these polymergroups, can be applied not only directly on the sanitary object, adheresthere and can be flushed away only after a relatively large number offlushing operations, but, as a consequence of its stickiness, can alsoserve to attach bar-shaped agents to the toilet bowl.

The special adhesion promoters mean that the agent adheres to thesanitary surface and that further materials such as bar-shaped agents,for example with cleaning or deodorizing active ingredients, can bestuck to the surface of the adhesive. Moreover, these adhesion promotersare characterized in that the agents comprising these adhesion promoterscan be flushed away without residue and that the agents comprising theseadhesion promoters are insensitive towards fluctuations in the mixingratio of adhesion promoter to filler.

By adding suitable fillers it is possible, for example, to adjust theviscosity and/or the flushability of the agent and to achieve thedesired deodorization or coloring of the agent.

A broader field of use is opened up by the agent according to theinvention:

In the case of the use of a water-soluble adhesion promoter, the agentcan firstly be used as a water-soluble, temporarily adhering adhesivefor attaching bar-shaped cleaning agents, e.g. in the form of extrudedshaped bodies, in the toilet bowl, meaning that no special holdingdevices are required for these cleaning agents.

In this application of the agent as “pure adhesive”, the agent serves asreplacement for the WC cages perceived as unhygienic by the consumer. Onthe adhesive applied to the toilet bowl surface it is possible to attachbar-shaped agents comprising active ingredients having their ownfunctionalities such as conventional rim blocks with one or more phases,rim blocks with scented phase, deodorization tablets, rim blockscontaining bleach etc., where the adhesive replaces the WC cage in anhygienic manner and is gradually flushed away by the stream of flushwater together with the bar-shaped agent adhering thereto. It is ofcourse also possible for tablets compacted from powders or granules orelse water-soluble or water-insoluble plastics containing activeingredients to be attached to the adhesive.

In this application, the agent has at least one of the adhesionpromoters according to the invention and a thickener. Since the adhesionpromoters according to the invention are generally viscous liquids, theaddition of a thickener as filler is required so that the agent has thedesired high viscosity of at least 30 Pas. Since the adhesion promotersaccording to the invention are water-soluble, in this embodiment, theaddition of surfactants for increasing the ability to be flushed away isnot required.

Further constituents such as dyes, fragrances, optionally surfactants,foamers etc. can of course also be added to this basic formulation ofadhesion promoter and thickener.

In one modification of the first embodiment, besides the adhesionpromoter and the thickener, the agent also has perfume so that it can beused simultaneously for adhesion and for deodorization.

In the second application, the adhesive has the adhesion promotersaccording to the invention and, as filler, surfactants, meaning that itcan itself take on the cleaning function as a result of the suitableselection of the type and concentration of the surfactants andoptionally further additives. The adhesive effect facilitates the fixingof further desired active ingredients in the toilet bowl, e.g. of afragrance, of a bleaching tablet, of a descaling tablet, of anadvertizing medium etc.

With the cleaning adhesive, the consumer can thus, for example, select ascent corresponding to his current wishes and press the correspondingdeodorization tablet onto the applied cleaning adhesive such that itsticks firmly to the adhesive, for example in order to deodorize thetoilet for the next 1 or 2 weeks.

The adhesive according to the invention thus even makes it possible tooffer the adhesive together with a series of deodorization tablets ordeodorization gels, bleaching tablets, descaling tablets, intensivecleaning tablets etc. in a combined set and thus to make it possible forthe user to individually equip the adhesive.

If the consumer would like additional bleaching, then, for example, ableaching tablet is stuck onto the surface of the adhesive.

If the consumer would like particularly powerful and intensive cleaningof the toilet, then another cleaning tablet can additionally be stuckonto the cleaning adhesive. The build-up of multilayered agentsconsisting of the layers adhesive-functionality-adhesive-functionalityis also possible.

In contrast to this, although the agents known hitherto and described atthe start exhibit a good and lasting adhesion on the sanitary object, a“sticking on” of another agent is not possible with the adhesivesanitary agents known hitherto.

Besides use in the field of toilet hygiene, the agent can also be usedas cold adhesive which, as a result of the added surfactants, can beflushed away with water. The agent can be used as cold adhesive in thesanitary sector, e.g. for the attachment of objects in urinals, but alsoin handwashing basins or on tiles in the shower, or else in kitchens,restaurants, slaughter houses or other places where water is used forrinsing.

By using the cold adhesive in places where water is used for rinsing, atthe same time as rinsing away the adhesive, cleaning also takes place asa result of the surfactants present in the adhesive.

Likewise conceivable is the use of the agent according to the inventionin washing facilities for the cleaning of motor vehicles or forapplication on/in drains or gullies, for example in order to temporarilydeodorize these.

The agent according to the invention can also be used as a wash-offpaste for accommodating bait to combat vermin or for attachment towindows or facades which are rained on, so that the agent is consumedgradually.

The individual constituents of the agent according to the invention aredescribed below:

A preferred class of the non-water-soluble adhesion promoters from thegroup of polyalkylene derivatives includes polyalkylene chains withrandomly distributed functional groups. The polyalkylene chains arepreferably polybutadiene, polyisopropylene and polypropylene chains.

The functional groups randomly distributed over the polyalkylene chainsare preferably reactive groups, in particular from the group ofanhydrides, thiols, epoxides or primary amines.

Particular preference is given to polymers with maleic anhydride groupsbonded randomly to the polybutadiene chain. The particularly preferredmaleic anhydride adduct onto 1,4-cis-polybutadiene is available fromDegussa under the name Polyvest.

Furthermore, as non-water-soluble adhesion promoters it is possible touse silicone systems, for example from the group of constructionsilicones eliminating acetic acid (acetate system).

Such organopolysiloxane mixtures also known as cold-vulcanizing,single-component silicone rubbers, usually crosslink at room temperaturewith absorption of water from the surrounding atmosphere to giverubber-elastic polymers. The chain extenders and crosslinkers used aredi- and preferably polyfunctional acetoxysilane compounds whicheliminate acetic acid as a result of reaction with the polysiloxane oras a result of hydrolysis and thus initiate the formation of amacromolecular network.

Of suitability in principle as adhesion promoters are, however, also thesilicone systems based on amine/aminoxy systems, oxime systems,benzamide systems and alkoxy systems, provided these can be stabilizedwith the additional system components described hereinbelow to givehomogeneous, stable mixtures.

Furthermore, olefin homopolymers and copolymers of two and more olefinswhich, are partly oxidized or further functionalized via graft moleculescan be used as adhesion promoters. These compounds include, for example,the polybutadiene rubbers, the styrene-butadiene block polymers andcopolymers, and the polyisopropenes if they are partly oxidized orfurther functionalized via graft molecules. It is also possible to usethe “random (block) polymers” which are prepared by 1,3-addition ofbutadiene or isoprene onto styrene or alpha-methylstyrene, thehomopolymers or copolymers of ethylene and propylene, such as theethylene-propylenediene terpolymers, ethylene-ethylene oxide copolymers,natural rubber and norbornene polymers such as polydicyclopentadiene ifthey are partly oxidized or further functionalized via graft molecules.

As water-soluble adhesion promoters it is also possible to usecopolymers from the group of monoalkyl esters of poly(methyl vinylethers/carboxylic anhydrides, which are commercially available, forexample, under the trade name Gantrez from ISP.

A further preferred class of the water-soluble adhesion promoters arethe polyalkyleneimines, i.e. polymeric amines or polymers whichcomprises polyimine groups.

The class of polyimines includes in particular the homopolymericpolyalkyleneimines of the general formula —(R—NH)_(n−) where R=alkyl oralkyl derivative, n=10-10⁵ and two- or three-dimensional crosslinkingvia the nitrogen function, depending on the degree of alkylation orarylation on the nitrogen.

A preferred class of the polyalkyleneimines are the polymeric sphericalpolyalkyleneimines which are based in particular on homopolymericpolyethylene with a certain ratio between primary, secondary andtertiary amine functions. These polyethyleneimines can quaternize withwater or acids, i.e. form polycations.

Of course, besides the ethylene group, the polyalkyleneimines can alsocontain methylene, propylene, butylene or higher alkylene groups asalkylene group.

Polyalkyleneimines are available for example from BASF under the tradename Lupasol with different molecular masses and degrees ofcrosslinking.

In principle, the polyalkyleneimines can also be present in derivatizedform and/or as cationic polymers.

Polyalkyleneimines are soluble in water and other polar solvents.

Similarly, these polyimines can also be used in alkoxylated, inparticular ethoxylated or propoxylated, form.

Likewise suitable as adhesion promoters are the so-called polyetheramines (alkoxylated amines), which are likewise water-soluble.

These are in particular ethoxylated or propoxylated primary and/orsecondary and/or tertiary alkyl- or arylamines. The alkyl or arylradical may be branched such that then (formally) di-, tri- or oligo- orpoly(EO/PO)-amines are formed. The alkoxylated polyamines enter intotypical amine reactions with other functional groups (amide formation,urea analogs, imine formation with carbonyls etc.).

Preferably the alkoxylated polyamines are selected from the group ofpolyether amines. The polyether amines may include tri-, bi- and/ormonofunctional primary amines and, as polyether groups, polyethyleneoxide groups, mixed poly(ethylene oxide/propylene oxide) groups orpolypropylene oxide groups, the hydrophilicity of the polyether aminesdecreasing in this sequence. However, it is of course also possible forthe alkoxylated amines to have other polyether groups, such as, forexample, polybutylene oxide groups.

Polyether amines with diamines or polyether amines with secondary aminescan likewise be used.

Polyether amines are available for example from Huntsman, USA under thetrade name Jeffamine® T-5000.

The molar masses of the polyether amines can vary over a wide range.Within the context of the present invention, in particular polyetheramines with molar masses between 500 and 5000 have been used.

On account of the comparatively low viscosity of the alkoxylated amines,it is necessary to add viscosity-increasing substances, such as, forexample, pulverulent surfactants, polysaccharides (wood flour, starch,meal) lignin etc., as fillers, to the agents according to the invention.

Furthermore, derivatives of the polyimines which can be used are alsothe ethoxylated polyimines according to the formula below, i.e. thesystems which are obtainable by ethoxylation of the polyimines:

-   where R₁=alkyl or alkyl derivatives;-   R₂, R₃=(—CH₂—CH₂—O)_(n)—R₄ or (—(CH₂)₃—O)_(n)—R₄-   R₄=H, alkyl, aryl; n=1-100

Derivatives of the polyimines which can likewise be used are compoundswhich are obtainable by reaction at the nitrogen function, such as, forexample, polyurethane derivatives etc., i.e.

-   R₂, R₃=C(O)—N—X-   where X=copolymer, e.g. polyurethane, i.e. the side radical attaches    again to a polymeric chain (imine quasi as copolymer of a block    polymer) in the above formula (1).

Furthermore, according to the invention, polyglycerol polyetheralkylcarboxylic acids can also be used as water-soluble adhesionpromoters. These are polyether alkylcarboxylic acids which areesterified via glycerol, such as, for example, polyethylene glycol-150polyglyceryl-2 tristearate or PEG-150 diglyceryl tristearate or PEG-150tetraglyceryl distearate, where PEG-150 polyglyceryl-2 tristearate ispreferred.

The polymer consists of a polyglyceryl backbone to which fatty acidradicals are attached via flexible PEG chains.

The thickening effect is presumably based on an associative interactionof the fatty acid radicals of PEG-150 polyglyceryl-2 tristearate withthe surfactant micelles in the formulation. As a result of physicalinteraction, a 3-dimensional network could be spread out, which leads tothe increase in viscosity in the aqueous surfactant system (for examplea flushing operation in the toilet). The structure of the polymer, i.e.the polarity of the fatty acid ester (carbon chain length), the lengthof the flexible spacer (degree of ethoxylation of the PEG) and thestructure of the backbone (number of glycerol units) have an influenceon the thickening properties.

It is of course also possible to use combinations of the aforementionedadhesion promoters in the agent according to the invention.

As regards the selection of the adhesion promoters, their reactivityshould also be taken into consideration. Within the context of thepresent invention, no particularly reactive polymeric startingcompounds, such as, for example, reactive silicone masses, should beused as adhesion promoters since these always polymerize further and asa result always become more viscous. Also, systems based on polyurethaneor with epoxide-containing starting compounds react too rapidly andbecome viscoelastic upon mixing. These systems adhere only slightly orno longer at all.

The adhesion promoter brings about the adhesion of the agent to thesurface of the sanitary object. The agents according to the inventionadhere both to dry surfaces and also to damp surfaces.

Furthermore, the special adhesion promoters also lead to the appliedagent being sticky on its surface, such that other active ingredientagents can be stuck onto the surface of the adhesive.

In general, the adhesion promoter also forms network-like structureswhich impart the required dimensional stability to the agent even underthe effect of strong force as a result of flushing water.

The concentration of the adhesion promoter to be used is dependent onthe particular substance class and the ability of the adhesion promoterto form a network and is generally between 2% by weight and 60% byweight, preferably between 7% by weight and 50% by weight andparticularly preferably between 8% by weight and 40% by weight.

Furthermore, the agent according to the invention comprises fillers,which can be selected from the group of surfactants, thickeners,fragrances, dyes, salts, foam stabilizers, foam boosters, foamgenerators and polymeric natural substances.

In principle, surfactants which can be used are all known anionic and/orcationic and/or nonionic and/or amphoteric surfactants, preference beinggiven to pulverulent to highly pasty ones. The surfactant fraction inthe agent should be between 0% by weight and 80% by weight, preferably10% by weight to 60% by weight and particularly preferably 25% by weightto 45% by weight.

The anionic surfactants take on several tasks in the present invention;firstly, they serve, in the case of polymeric water-insoluble matrices,to emulsify the polymeric matrix without completely destroying theadhesiveness. Secondly, they make a significant contribution to theplastication of the starting polymer (adhesion promoter), by serving asviscosity increaser (thickener). Preferably, the anionic surfactantsshould also be highly-foaming in order to indicate visually a cleaningeffect e.g. in a toilet bowl. Last but not least, a good cleaning effectof the surfactants is desired which is supported by the good wettingproperties.

As anionic surfactants, preference is given to using one or moresubstances from the group of the salts of carboxylic acids, of sulfuricacid half-esters and of sulfonic acids, preferably from the group offatty acids, fatty alkylsulfuric acids and alkylarylsulphonic acids.Usually, the carbon chain distributions of the anionic surfactants arein the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22carbon atoms.

Carboxylic acids (C6-C22) in the form of their metal salts (preferablyalkali metal salts) and their natural or synthetic mixtures and alsoalkali metal salts of sulfuric acid half-esters and relativelylong-chain alcohols can likewise be used as anionic surfactants.

A further class of anionic surfactants which can be used according tothe invention are the alkali metal salts of alkyl ether sulfuric acids.Alkyl ether sulfuric acids are, like alkylsulfuric acids, synthesizedfrom fatty alcohols, which are reacted with ethylene oxide to give thefatty alcohol ethoxylates in question. Instead of ethylene oxide, it isalso possible to use propylene oxide. The subsequent sulfonationproduces the alkyl ether sulfuric acids in question.

The alkali metal salts of alkanesulfonic acids and olefinsulfonic acidscan also be used as anionic surfactants within the context of thepresent invention. Alkanesulfonic acids can contain the sulfonic acidgroup in terminally bonded form (primary alkanesulfonic acids) or alongthe carbon chain (secondary alkanesulfonic acids). Typicalrepresentatives are alkylbenzenesulfonates, particularly preferablylinear alkylbenzenesulfonates (LAS).

The aforementioned anionic surfactants can be used in their neutralizedform alone or in a mixture with one another.

According to the invention, the surfactant phase comprises, based on itsweight, preferably 10 to 90 and particularly preferably 40 to 85% byweight of lauryl sulfate.

In adhesives with the thin-liquid adhesion promoter based on butadienederivative, the anionic surfactants simultaneously also serve asthickeners.

Nonionic surfactants which can be used are alkoxylated, preferablyethoxylated, in particular primary alcohols having preferably 8 to 18carbon atoms and on average 1 to 12 mol of ethylene oxide (EO) per moleof alcohol, in which the alcohol radical may be linear or preferably2-methyl-branched or can contain linear and methyl-branched radicals ina mixture, as are usually present in oxo alcohol radicals. Inparticular, however, alcohol ethoxylates with linear radicals fromalcohols of native origin having 12 to 18 carbon atoms, e.g. fromcoconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol andon average 2 to 8 EO per mole of alcohol are preferred. In addition tothese nonionic surfactants, fatty alcohols with more than 12 EO can alsobe used. Examples thereof are tallow fatty alcohol with 14 EO, 25 EO, 30EO or 40 EO.

Moreover, further nonionic surfactants which can be used are also alkylglycosides of the general formula alkyl-O(G), where alkyl is a primarystraight-chain or methyl-branched, in particular 2-methyl-branched,aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, andG is the symbol for a glycoside unit having 5 or 6 carbon atoms,preferably glucose.

A further class of preferably used nonionic surfactants, which are usedeither as the sole nonionic surfactant or in combination with othernonionic surfactants, are alkoxylated, preferably ethoxylated orethoxylated and propoxylated fatty acid alkyl esters, preferably having1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methylesters. Nonionic surfactants of the amine oxide type, for exampleN-cocoalkyl-N,N-dimethylamine oxide andN-tallow-alkyl-N,N-dihydroxyethylamine oxide or alkanolamides can alsobe used.

The fraction of the nonionic surfactant(s) in the overall surfactantphase can be up to 50%, preferably up to 30% and particularly preferablyup to 25%.

The surfactant phase can, if desired, also be equipped with cationic oramphoteric and zwitterionic surfactants. Examples of amphotericsurfactants are fatty acid amidopropylbetaines with C5-C21 fatty acidfractions, but also amphodiacetates.

Cationic surfactants are preferably used in acidic formulations incombination with bactericidal substances. Zwitterionic surfactants canbe described by way of example as quaternary ammonium, phosphonium orsulfonium components which are joined, via an aliphatic bridge, to afurther now anionic group such as carboxy, sulfonate, sulfate, phosphateor phosphonate.

Furthermore, olefinsulfonates, ether sulfates or acid methyl tauridescan be added as foamers to the agent. If strong foamers are to be used,then preferably 1 to 50, in particular 1-25% of the surfactant phase canbe replaced by one or more foamers, e.g. from the group of betaines,alkoxylated alkyl ether sulfates or lactobionic acid derivatives. Thesefoamers can be selected from the fatty acid amidopropylbetaines with aC5-C21-fatty acid fraction such as, for example, cocoamidopropylbetaine,the alkali metal or ammonium salts of lauryl ether sulfates with 1 to 5EO, lacto-bionococoylamide, lactobionooleylamide, lactobiono-talgamideetc. or mixture thereof. These foamers can be incorporated easily intothe pressure-sensitive adhesive. Preference is given to using thosecosurfactants which are present in solid, preferably pulverulent orhigh-viscosity form.

Besides the constituents according to the invention, the adhesive cancomprise further customary constituents, for example salts,disinfectants (e.g. oxygen or chlorine donors), preservatives, such as,for example, isothiazolone derivatives, foam stabilizers such as, forexample, alkanolamides, hydrophobicizing agents such as, for example,mineral oils or (partially) methylated siloxanes and silanes, calciumdispersants such as sodium salts of polycarboxylic acids or dyes.

By adding perfume oil or fragrances, the adhesive can also be used fordeodorizing the air.

Perfume oils and fragrances which can be used are individual odorantcompounds, e.g. the synthetic products of the aldehydes, alcohols,esters, ethers, ketones and hydrocarbons. Odorant compounds of the estertype are e.g. benzyl acetate or benzyl formate. The ethers include, forexample, benzyl ethyl ether, the aldehydes include e.g. citronellal, theketones include α-isomethylionone, the alcohols include citronellol,eugenol, geraniol and linalool. The hydrocarbons include primarily theterpenes such as limonene and pinene. However, preference is given tousing mixtures of different fragrances which together produce thedesired scent note. These also include those perfume oils which comprisenatural odorant mixtures, as are accessible from vegetable sources, suchas e.g. pine oil, citrus oil, lavender oil, mint oil or oil from orangepeel.

The fragrances are incorporated directly into the batch inconcentrations between 0.25% by weight and 20%, preferably between 3% byweight and 15% by weight and particularly preferably between 5% byweight and 10% by weight.

If desired, salts such as, for example, sodium sulfate can also be addedto the formulation as fillers, for example in order to increase thedissolution rate. In the case of particularly cost-effective product,the salt fraction can be up to 90% by weight. In general, the saltfraction is up to 10% by weight, preferably up to 5% by weight. Suitablesalts are alkali metal salts of strong acids, such as sodium sulfate,sodium chloride or else sodium polyphosphate. It is likewise possible touse the alkali metal salts of the mono-, di- and polycarboxylic acids,but also alkaline earth metal salts of strong acids, such as calciumsulfate or salts of carbonic acid.

Calcium salts can be used in particular for increasing the service livesof the agent since they form, for example with the maleic anhydrides ofthe adhesion promoters based on polybutadiene derivative, polysoapswhich in turn have a hydrophobicizing effect and stabilize the entiresystem with the formation of calcium soap networks on the surface andthus counteract an ability to be flushed away.

In the event of excessive hydrophobicization of the agent through theformation of calcium polysoaps, in order to increase the ability to beflushed away, calcium soap dispersants, such as e.g. ampho-dipropionates(Lonza KL grade) or maleic acid/acrylic acid copolymer Na salts (BASFSokalan grades such as Sokalan CP5 or CP45) can be added to the agent.

Moreover, all dyes which do not have marked substantivity towards thesurfaces to be treated with the dye-containing agents can beincorporated as fillers into the agent. If water-soluble dyes are usedin the formulation and the latter then comes into contact with water asa finished product, e.g. upon flushing with water in a toilet bowl,interesting color progressions can be achieved which can also becorrelated with marketing arguments. For example, a slow blue coloration(from pale blue to deep blue) can indicate the slow activation of anactive ingredient up to its maximum activity.

Similarly, the adhesive can also be rendered acidic and comprise, forexample, substances which dissolve lime scale or urine scale (acids) asfillers.

Furthermore, (co)thickeners can be added to the agent according to theinvention in order to increase the plasticity of the agent.(Co)thickeners which can be used are, for example, bentonites, powdersurfactants, xanthans, polybutadiene rubbers, polyisopropenes, blockcopolymers, which contain linked oligomers consisting of oligo- orpolyethylene oxide and/or oligo- or propylene oxide and/or oligo- orpolybutylene oxide, and also aryl ethoxylates or alkyl-aryl ethoxylates.The polymeric natural substances such as the lignins or their alkalimetal or alkaline earth metal salts can also be used as (co)thickeners.

One preferred group of (co)thickeners is the hydrophilic xanthans.Through their use, a very hydrophilic compound is introduced into theagent which, upon sticking the agent onto a damp surface, immediately“sucks up” the water.

Furthermore, hydrophobicizing agents such as, for example, Aerosil, inparticular thoroughly methylated Aerosil (Carbot Carbon) can be added asfillers to the adhesive.

If an increase in the rate of adhesion should be desired, so-calledtackifiers, in particular from the class of hydrocarbon resins, naturalresins such as tall resin or balsam resin, or polyterpene resins, canalso be added as fillers to the agent.

In order to counteract unpleasant odors, the adhesive can also comprisemalodor counteractants, which are preferably added to the fragrances.Such malodor counteractants are described, for example, in U.S. Pat. No.7,288,507 B2.

The adhesive according to the invention can be applied and replaced in ahygienic manner without touching possibly contaminated devices attachedto the WC bowl.

An essential advantage of the agent according to the invention is thatit can be portioned as the consumer desires and/or can be supplied indifferent portion packs. The adhesive can be applied for example bymeans of an application syringe or by application of preportionedamounts by means of suitable devices. These application devices may befor example “clip systems”, grippers or small plates removable fromfilms, dispenser systems with pretensioned elements which fire acorresponding portion e.g. onto a ceramic surface.

The agent according to the invention can also be applied in a simplemanner at the same time to different places on the sanitary object, forexample in order to stick on two or more active ingredients which, indirect vicinity, would adversely affect one another in their effect,such as, for example, a deodorizing tablet and a bleaching tablet.

The achieved adhesion to the sanitary object, even in the case ofapplication to a vertical surface, is so good that the agent does notcome off even under the additional action of force of streams of flushwater.

The adhesives according to the invention can only be flushed away aftera relatively large number of flushing operations. The number of flushingoperations is naturally governed by the composition of the particularagent, the amount applied and the geometry of the applied agent and isgenerally, for an application with a thickness of 2 to 5 mm, between 50and 150, in particular more than 120, flushes.

If the agent is used as adhesive in the toilet bowl, the durability isessentially defined via the flush-away time of the applied further body(bar-shaped agent). In the case of a conventional toilet block, thus aservice time of from 100 to 200, in many cases >250 flushes, can beachieved, the adhesive agent being gradually washed away together withthe stuck-on material. The applied amount is 3 to 15% by weight, inparticular 5 to 10% by weight, of the mass of the stuck-on agent.

Preferably, the agent according to the invention is white,ointment-like, pasty and/or cream-like and dimensionally stable so thatit does not “run off” or “drip”.

The adhesion and also the shape of the agents is retained despite theconsiderable forces (friction, deformation, shear effect) which act as aresult of the water flushing.

The agent essentially exhibits pseudoplasticity, i.e. the viscositydecreases with increasing shear forces.

If the shear rates are low, however, a severe flow constraint isobserved; moreover, the viscosity curves at a shear rate ramp between2.5 s⁻¹ and 30 s⁻¹ show the appearance of local maxima. There areevidently areas of differing viscosity or the agent changes itsstructure over the short measurement time (ramp time 100 sec).

The viscosities of these agents, to be determined using a Haakeviscometer, plate/plate system, plate diameter 10 mm at a shear gradientof 2.62 s⁻¹ and 20° C., should be at least 30 Pas, preferably at least45 and particularly preferably at least 100 Pas. Preferably, theviscosities should be between 150 or 300 and 6000 Pas and particularlypreferably between 200 and 1000 or between 1000 and 4000 Pas.

Preferably, the agents according to the invention which comprisesurfactants produce a finely-bubbled foam which can be adjusted inrespect of its volume by suitable additives (foam boosters). The foamnumbers of the agents according to the invention should be more than 40ml of foam. Particular preference is given to agents with foam numbersof >60 ml, very particular preference being given to foam numbers of 140ml or even more than 200 ml.

The surface tension of the agents can be between 50 and 65 mN/m.Preference is given to those agents whose surface tension is ≦60 mN/m.Particular preference is given to agents which achieve surface tensionsequal to or less than 40 mN/m. The surface tension is a measure of thewetting of the surface. The lower the surface tension, the better thesurface is wetted. A good wetting effect is a prerequisite for a goodcleaning performance of the agents under consideration.

The agent according to the invention is prepared by stirring thecomponents together at room temperature.

The invention is described below by reference to various embodiments andexperiments.

Table 1, which is attached at the end of the description, lists variousformulations of the adhesives according to the invention.

The flush numbers in table 1 were determined on applied amounts of 2-5g.

Table 2, which again is attached at the end of the description, liststhe starting materials used for producing the agents according to theinvention in table 1.

All of the adhesives of the invention according to formulations V13 toV38 exhibit strong adhesion and are so sticky on their outside thatconventional toilet cleaning agents with a mass of up to 50 g can bestuck onto the agents depending on what amounts of adhesive are applied.The ratio of stuck-on mass of the bar-shaped agents to the adhesive masshere is at most 100:1, preferably at most 50:1 and particularlypreferably at most 10:1. Better adhesion of the agent is naturallyachieved if the adhesive surface is larger. The customary adhesivesurfaces are between 1000 mm² and 800 mm² (full-area contact). However,they may also be less than 400 mm² if the adhesive is applied in theform of circular beads.

In all of the flushed-off experiments, the surfactants used were anionicsurfactants. The flush numbers of these agents exhibit relatively highto high service lives.

V20 is a formulation for an acidic agent. The lower flush numbers ofthis agent are presumably due to the fact that, as a result of the lowpH, no lime soaps (which increase the flush numbers) are formed.

Formulations V23a, V29 and V30 comprise only one (anionic) surfactantand an adhesion promoter. These agents consisting only of two componentsalso exhibit the desired adhesion, the required stickiness and flushnumbers of more than 100.

Compared to this, the applied pure adhesion promoter Polyvest 800 S(1,4-cis-butadiene maleic anhydride adduct), a thin-liquid product,immediately runs down on the toilet bowl and exhibits no adhesion.Sticking on a customary toilet block of 50 g, 30 g, 10 g, 5 g is notpossible on the pure adhesion promoter Polyvest. The bar-shaped agentimmediately falls down; no adhesive effects are observed.

Table 3, which is likewise attached at the end of the description,summarizes the results of various adhesion experiments carried out usingthe agents of the invention according to table 1.

To carry out the adhesion experiments, either the stated defined amountof adhesive agent (adhesive) was coated onto the reverse of the samplebody to be firmly attached through adhesion, or the adhesive was appliedto one surface of the sample body using a spatula to a thickness of ca.2-4 mm.

The sample body was then stuck directly into a ceramic toilet bowl. As arule, the sample bodies were stuck to the damp front inside surface ofthe toilet using slight pressure. Adhesive agents and sample bodies areimmediately ready for use and can be directly flushed over.

The experiments in table 3 demonstrate that the adhesive agentsaccording to the invention containing the adhesion promoter Polyvest,the 1,4-cis-polybutadiene maleic anhydride adduct, not only adhere tothe sanitary bowl, but also have such good adhesive properties that theyare suitable for the sticking on of toilet blocks, descaling tablets,transparent soap systems etc. in the bowl.

Comparing the adhesion behavior of the systems of the presentspecification with the systems from WO 99/66017, it can be establishedthat the latter enter into no kind of adhesive function with the samplebodies listed in table 3.

As soon as it is attempted e.g. to attach a customary toilet block tothe surface of the gel from WO 99/66017, the latter immediately slipsdown on account of gravity. Consequently, no kind of durable adhesivefunctionalities are built up.

On the part of the applicant, it is assumed that the good adhesiveproperties of the present Polyvest-based agents are due firstly to thepresent randomly distributed maleic anhydride groups, which bring abouta chemical adhesion with functional groups on the surface of the carrier(reactive adhesive); on the other hand, however, this effect might alsocontinue inwards and the maleic anhydride groups react with functionalgroups in the structure (e.g. with the nucleophilic groups of thesurfactants and cothickeners involved) (cohesion effect), such that moreor less extended structures analogous to the glyptal resins are probablyformed.

The starting substance in pure form is also already a pressure-sensitiveadhesive which has lasting stickiness over a long period (until thereactive groups are cured). However, such a pure adhesive (withoutsurface-active fractions) can only be removed from a ceramic surfacewith great difficulty, if at all.

The cohesion effect of the maleic anhydride function should increasee.g. in the case of long-chain fatty alcohols or in the case oflong-chain PEG systems (e.g. Polyox WSR 303) which are also incorporatedinto the formulation.

A first indication of said interaction is given in experiment V22 incombination with the V2 block (table 3). The formulation of the V2 blockproduces flush numbers of more than 460 for a significantly smallersample body.

In addition to the crosslinking processes, in the case of the presentformulation, the formation of polysoaps from the calcium ions can alsoplay a role, which leads to greater hydrophobicization of the entiresystem and thus to poorer solubility in water.

A further contribution to increasing the forces of adhesion is expectedby the xanthan involved. The rapid formation of hydrocolloids uponcontact with the aqueous surfaces in the toilet system results in rapidwater removal on the surface. Consequently, other, e.g. adhesive,interactions of the adhesive with a pseudodry ceramic surface canrapidly be established.

As a consequence of these overall interactions, the adhesive compoundsremain stuck to the surface of a ceramic object for a relatively longtime, even if it is flushed over with water. This is all the moresurprising since the water in the flushing operations ought to actuallyback-migrate the surfactant-containing agent (with good wetting numbers)and thus lead to detachment from the ceramic object.

In the present system, it is even the case that the adhesive mass or asecond component stuck on therewith is eroded from the outside inwards.

Table 4, which is attached after the description, lists by way ofexample the foam numbers and surface tensions of a number of agentsaccording to the invention from table 1.

Table 4 shows that the agents according to the invention differsignificantly from the agents known hitherto from EP 1325103 B1. Thepresent agents are thus significantly better foamers.

To determine the foam numbers, 100 ml of the stock solution thermostatedat 20° C. are transferred to a 250 ml mixing cylinder, which is closedwith a PTFE stopper. The cylinder is then moved to and fro twenty times(inverted 20 times). After in each case 30 sec/5 min/30 min, thegenerated foam volume (ml) is read off and noted.

The surface tensions were determined using the BP 2 instrument fromKrüss bubble-pressure measuring instrument.

When checking the blank value, the procedure was as follows: using theUfaryl DL 90 C a 0.1% strength solution is prepared, at 20° C. ameasurement curve is recorded three times with the capillary diameterascertained beforehand and averaged. The deviation from the average mustbe not more than 1 mN/m.

The first test is taken as initial value, all of the subsequent testsare compared with the initial value (50/100/500 ms). In the event ofdeviation greater than ±2 mN/m, the capillary is exchanged for a newone.

For the measurement, the surface tension of a 0.1% strength solution(20° C.) was ascertained as a function of the age of the surface. Thesurface tension after 100, 500, 1000 ms is observed here.

Table 5 lists various formulations of the adhesive agents according tothe invention containing polyalkyleneimines as adhesion promoter, andtable 6 lists alkoxylated amines and polyglycerol polyetheralkylcarboxylic acids.

TABLE 5 Amount [g] Sample Sample No. Sample No. No. Sample No. 100 101102 103 Tensopol USP 94 8.00 8.00 8.00 8.00 Marlinat 4.50 4.50 242/90TOrange Fun 2.05 2.05 2.05 2.05 Kelzan ASX 0.16 0.16 0.16 0.16 Sodiumsulfate 70.0 Lupasol SK 5.92 Lupasol P 5.90 Genapol DAT 5.92 1.50 EmanonXLF 1.50 1.50 Sum 16.13 16.11 92.13 17.71 Initial weight Percentage 36.336.6 8.1 16.9 fraction of the adhesion promoter Viscosity [Pa s] 47 1906710 317 Foam value [30 s, 100/90/60 125/110/90 80/60/40 160/140/130 5min, 30 min] Bubble pressure 53/46/43 59/51/47 63/54/50 49/40/37 [100,500, 1000 ms] Flush number upon 1 95 160 57 application of the puremass* Flush number, 12 128 180 120 application of the mass to block**Adhesion base dry and dry and wet wet wet wet *application was carriedout using an applicator with a narrow rectangular opening in a stripe ofwidth ca. 2 cm and thickness ca. 3 mm. **the agent was applied to atoilet block, the applied amount was ca. 10% of the weight of the toiletblock. The toilet block was then stuck to the sanitary surface by theagent. Tensopol USP 94 is a surfactant (C12-C16 lauryl sulfate),available from Manro. Marlinat 242/90T consists of C12-C14-alcoholpolyethylene glycol and propylene ether (2 EO) sulfate, glycoltriisopropanolammonium salt (Sasol). Orange Fun is a perfume, availablefrom Givaudan. Kelzan AS is a xanthan (thickener/cothickener), availablefrom Kelco. Genapol DAT is PEG-150 polyglyceryl-2 tristearate and PEG-6capryl/capric glyceride. Lupasol SK is a liquid polyethyleneimine with amolar mass of ca. 2000000 available from BASF, Lupasol P is a liquidpolyethyleneimine with a molar mass of ca. 750000 available from BASF.

TABLE 6 Amount [g] Sample Sample Sample Sample Sample Sample No. No. No.No. No. No. 104 105 106 107 108 109 Tensopol 10 6 8 8.50 12.00 8.00 USP94 Marlinat 4.80 4.50 4.50 2.25 4.50 242/90T Orange 2 2 2.05 2.05 2.052.0 Fun Kelzan 0.15 0.15 0.16 0.16 0.16 0.15 ASX Emanon 1.50 1.50 1.501.50 1.50 XLF Jeffamine 6.00 6.00 5.94 T 5000 Jeffamine 3.00 5.94 ST-404Chalk 2.50 (CaCO₃) Cab-Osil 1.50 Arboform water- soluble Hydriol 6.61PGR Sum 26.95 21.65 22.15 17.46 26.15 16.76 Initial weight Percentage22.2 27.7 26.8 17.2 22.7 39.4 fraction of the adhesion promoterViscosity 503.6 401 227 228 220 226 [Pa s] Foam value 170/ 130/ 210/200/ 45/ [30 s, 165/150 120/50 180/160 175/150 10/5 5 min, 30 min]Bubble 52.6/ 50/ 43/ 43/ 57/ pressure 43.9/41.1 42/40 35/33 35/33 48/45[100, 500, 1000 ms] Flush 21 84 70 49 43 71 number upon application ofthe pure mass* Flush 193 208 34 105 101 65 number, application of themass to block** Adhesion wet wet wet wet wet dry base wet Emanon XLF isglycereth-7 caprylate/caprate, available from KaO Corporation, S.A.Jeffamine T 5000 is a polyether amine, available from Huntsman, USA,with a molar mass of ca. 5000 (triamine which is prepared by reaction ofpropylene oxide with a triol initiator, followed by an amination of theterminal hydroxy groups). Jeffamine ST-404 is a modification of thepolyether amines with a molecular mass of ca. 565, available fromHuntsman, USA (secondary amine version, secondary triamine. The amineend groups are reacted with a ketone, e.g. acetone, and reduced).Cab-Osil is a highly disperse silica.

Arboform, water-soluble, is available from Tecnaro, Ilsfeld, Germany andis granules which consist of the polymers lignin or lignin derivatives,biodegradable polyesters, lignocellulose or lignocellulosic fibers andnatural resins, namely aliphatic and aromatic ketones, alcohols,carboxylic acids, lactones and polycycles in monomeric, oligomeric andpolymeric form.

Hydriol® PGR is polyglycerol polyricinoleate.

All of the investigated agents according to the invention adhere/stickexceptionally both to dry and to wet surfaces.

Also, they are so sticky on their outside that conventional toiletcleaning agents with a mass of up to 50 g or even more can be stuck ontothe agents, depending on what amounts of adhesive are applied. In all ofthe flushed-off experiments, the surfactants used were anionicsurfactants. The flush numbers of these agents exhibit relatively highto high service lives.

The surface tensions were determined using the BP 2 instrument fromKrüss bubble-pressure measuring instrument.

When checking the blank value, the procedure was as follows: using theUfaryl DL 90 C a 0.1% strength solution is prepared, at 20° C. ameasurement curve is recorded three times with the capillary diameterascertained beforehand and averaged. The deviation from the average mustbe not more than 1 mN/m.

The first test is taken as initial value, all of the subsequent testsare compared with the initial value (50/100/500 ms). In the event ofdeviation greater than ±2 mN/m, the capillary is exchanged for a newone.

For the measurement, the surface tension of a 0.1% strength solution(20° C.) was ascertained as a function of the age of the surface. Thesurface tension after 100, 500, 1000 ms is observed here.

The flush numbers were measured using a flush volume per flush of 8 land a flush rhythm of 19 flushes per day according to a defined scheme.The flush-water temperature during the short flush frequencies (forexample between the third and fifth flush) was 13° C. to 14° C. andduring the long resting periods (for example between the nineteenth andfirst flush) was 15° C. to 16° C. The temperature of the flush water waschecked on each work day and noted.

TABLE 1 V13 V14 V15 V17 V19 V19.1 V20 V22 V23a V29 V30 in g in g in g ing in g in g in g in g in g in g in g Tensopol 15.72 48.7 47.59 39.0938.4 37.37 42.55 40.72 69.75  20.39  29.67 surfactant USP 94 Polyvest37.80 38.22 32.77 31.3 30.43 35.1 30.96 30.25  79.61  70.33 adhesion800S promoter Calcium 17.19 14.9 16.87 salt sulfate (dihydrate)Bentonite 32.26 11.69 thickener Construction 39.44 thickener siliconeKelzan  1.07 0.91 0.95 0.83 0.7 0.7 0.8 1.02 thickener ASX Aerosil TS4.9 5.17 5.32 5.19 hydropho- 720 bicizing agent Blue color 0.0001 colorOrange 13.14 12.2 12.02 10.13 9.7 9.41 10.64 10.42 perfume Fun Citricacid 5.59 acid Total 99.99 100.03 100.00 100.01 99.90 99.95 100.00 100100 100.0 100.00 [in g] Flushes: >400 ca. 140 no ex- 120 >130 >250 72 94168 no ex- no ex- peri- peri- peri- ment ment ment V34 V35 V36 V37 V38in g in g in g in g in g Tensopol USP 36.99 37.22 37.08 36.90 37.13surfactant 94 Polyvest 800S 36.99 36.97 37.08 37.08 37.13 adhesionpromoter Calcium sulfate salt (dihydrate) NaCl 12.30 salt Sodium sulfate12.32 salt Bentonite thickener Construction silicone thickener KelzanASX 0.99 0.99 0.93 1.05 0.92 thickener Aerosil TS hydropho- 720 bicizingagent Blue color color Orange Fun 12.45 12.51 12.55 12.67 12.50 perfumeCitric acid acid Nonionic surfactant 12.58 surfactant Betaine 12.32surfactant Anionic surfactant 12.36 surfactant Total [in g] 100.00100.01 100.00 100.00 100.00 Flushes: no no no no no experimentexperiment experiment experiment experiment

TABLE 2 Manufacturer Grade Chemistry Function Bentonite Süd-ChemieOptigel CL Bentonite thickener Tensopol USP 94 Manro Tensopol USP 94C12-C16 lauryl sulfate surfactant Orange Fun Quest # F561415 perfumeConstruction Sales: Meister thickener silicone Werkzeuge/WerkzeugfabrikWuppertal, Wuppertal Aerosil TS 720 Carbot Carbon TS 720hydrophobicizing agent Kelzan ASX Kelco Kelzan ASX XanthanThickener/cothickener Polyvest 800S Degussa Polyvest 800S 1,4-cispolybutadiene, adhesion promoter maleic anhydride adduct Calcium sulfateKrone-Gips filler (dihydrate) Blue color Citric acid Jungbunzlauer acidNonionic Kolb Imbentin Fatty alcohol (30 EO) surfactant surfactantAG/168S300SP Betaine Goldschmidt Tego Betain CKD Cocamidopropylbetainesurfactant Anionic Sasol Marlon ARL Alkylbenzenesulfonate, Na surfactantsurfactant salt NaCl Solvay salt Na₂SO₄ Merck salt

TABLE 3 Flush No. Notes Adhesive material from experiment No. 22 1 V2block with Polyox 467 The V2 block consisted of 32% by wt. of anionicsurfactant, 6% by initial weight of block: 2.46 g wt. of sodiumcumenesulfonate, 43% by wt. of filler, 10.5% by wt. initial weight ofadhesive: 0.4 g of calcium sulfate, 0.5% by wt of Polyox WSR 303 resin(Union Carbide), 2% by wt of polyethylene glycol and 6% by wt. ofperfume 2 Standard 2 in 1 block 530 According to EP 1418225 B1, theextruded phase is the contact initial weight of block: 30.92 g phaseinitial weight of adhesive: 3.37 g 3 Standard yellow formulation 378According to EP 0844303 B1 initial weight of block: 11.13 g initialweight of adhesive: 2.41 g 4 Standard 2 in 1 block (bouquet) 90According to EP 1418225 B1; other embodiment; the gel phase is initialweight of block: 44.75 g the contact phase; initial weight of adhesive:1.28 g Adhesive material from experiment No. 19 5 Transparent soap 268according to DE 102007005617.8 Adhesive material from experiment No. 206 PP cage stuck into bowl 25 Standard commercial PP toilet cage 7Descaling tablet 7 Formulation according to DE 10333905 A1. The blockproduces CO2 with water and is therefore effervesced off from thesurface.

TABLE 4 Foam number [Pas], PP, 10 mm, [Pas], Senior PK 5, Experimentnumber [mm] 20° C., γ′ = 2.62 s⁻ 20° C., ¹γ′ = 0.3 s⁻¹ Surface tension13 foam (ml); n.d. 919 Surface tension (0.1%); (not determined) [mN/m];(0.1%); 30 sec/5 min/30 min 100 ms/500 ms/1000 ms 14 60/8/4 415 notmeasurable 64.6/56.9/53.3 19 40/20/10 2263 not measurable 55.9/47/44.223 40/12/3 5965 not measurable 60/51/47.4 31 n.d. 3382 not measurablen.d. Comparison gel from 70/25/10 524 n.d. 56.6/48.7/45.5 EP 1325103 B1

What is claimed is:
 1. A method for cleaning and/or deodorizing a toiletbowl or urinal comprising directly applying an agent to the toilet bowlor urinal, wherein the agent adheres to the toilet bowl or urinal andcan be flushed away only after a relatively large number of flushingoperations, wherein the agent comprises fillers from the group ofsurfactants and also an adhesion promoter, wherein the adhesion promoteris selected from the group of polyalkvlene derivatives which comprisepolyalkylene chains with randomly distributed functional groups, or fromthe group of copolymers from the group of monoalkylesters of poly/methylvinylethers/carboxylic anhydrides, olefin homopolymers and copolymers oftwo or more olefins being partially oxidized or further functionalizedvia graft molecules, and from the group of polyalkyleneimines,alkoxylated polyalkyleneimines, polyether amines or alkoxylated aminesand polyglycerol polyether alkylcarboxylic acids or polymers orderivatives containing these polymer groups, wherein the viscosity ofthe agent is at least 30 Pas measured using a Haake viscometer,plate/plate system, plate diameter 10 mm, at a shear gradient of 2.62s⁻¹ and 20° C. and the agent is so sticky that it can serve to attachbar-shaped agents to the toilet bowl or urinal, wherein theconcentration of the surfactants is between 10 and 80% by weight, andwherein the agent has associated therewith one or more bar-shapedcompositions selected from the group consisting of conventional rimblocks with one or more phases, rim blocks with scented phase, rimblocks containing bleach, compacted tablets, deodorization tablets,solid deodorization gels, bleaching tablets, descaling tablets orintensive cleaning tablets.
 2. A method for adhering an object to atoilet bowl or urinal, the method comprising directly applying an agentas cold adhesive to the toilet bowl or urinal, the object beingassociated with the agent, wherein the agent adheres to the toilet bowlor urinal and can be flushed away only after a relatively large numberof flushing operations, wherein the agent comprises fillers from thegroup of surfactants and also an adhesion promoter, wherein the adhesionpromoter is selected from the group of polyalkylene derivatives whichcomprise polyalkylene chains with randomly distributed functionalgroups, or from the group of copolymers from the group ofmonoalkylesters of poly/methyl vinylethers/carboxylic anhydrides, olefinhomopolymers and copolymers of two or more olefins being partiallyoxidized or further functionalized via graft molecules, and from thegroup of polyalkyleneimines, alkoxylated polyalkyleneimines, polyetheramines or alkoxylated amines and polyglycerol polyether alkylcarboxylicacids or polymers or derivatives containing these polymer groups,wherein the viscosity of the agent is at least 30 Pas, measured using aHaake viscometer, plate/plate system, plate diameter 10 mm, at a sheargradient of 2.62 s⁻¹ and 20° C. and the agent is so sticky that it canserve to attach bar-shaped agents to the toilet bowl or urinal, whereinthe concentration of the surfactants is between 10 and 80% by weight. 3.The method as claimed in claim 2, wherein the agent has a mass, whereinthe object has a mass, and wherein the mass of the agent applied to theobject is 3 to 15% by weight of the mass of the object.
 4. The method asclaimed in claim 1 or 2, characterized in that the polyalkylene chainsof the adhesion promoters from the group of polyalkylene derivatives areselected from the group consisting of polybutadiene, polyisopropyleneand polypropylene chains.
 5. The method as claimed in claim 4,characterized in that the functional groups are selected from the groupconsisting of anhydrides, thiols, epoxides and primary amines.
 6. Themethod as claimed in claim 4, characterized in that the polyalkylenederivatives are polymers with maleic anhydride groups bonded randomly tothe polybutadiene chain and preferably the maleic anhydride adduct onto1,4-cis-polybutadiene.
 7. The method as claimed in claim 1 or 2,characterized in that the adhesion promoter from the group of olefinhomopolymers and the copolymers from two or more olefins which arepartly oxidized or further functionalized are selected from the group ofpolybutadiene rubbers, styrene-butadiene block polymers and copolymers,polyisoprenes, random block polymers which are prepared by 1,3-additionof butadiene or isoprene onto styrene or alpha-methylstyrene,homopolymers or copolymers of ethylene and propylene, such asethylene-propylenediene terpolymers, ethylene-ethylene oxide copolymers,natural rubber and norbornene polymers such as polydicyclopentadiene. 8.The method as claimed in claim 1 or 2, characterized in that theadhesion promoters from the group of polyalkyleneimines arehomopolymeric polyalkyleneimines, in particular of the general formula—(R—NH)_(n) where R=alkyl or alkyl derivative, n=10-10⁵ with a two- orthree-dimensional crosslinking on the nitrogen function.
 9. The methodas claimed in claim 8, characterized in that the polyalkyleneiminescontain, as alkylene group, an ethylene, methylene, propylene, butyleneor higher alkylene group.
 10. The method as claimed in claim 1 or 2,characterized in that the polyether amines are alkoxylated primaryand/or secondary and/or tertiary alkyl- or arylamines.
 11. The method asclaimed in claim 1 or 2, characterized in that the polyether aminescontain tri-, bi- and/or monofunctional primary amines and, as polyethergroups, polyethylene oxide, mixed poly(ethylene oxide/propylene oxide)or polypropylene oxide groups.
 12. The method as claimed in claim 1 or2, characterized in that the polyglycerol polyether alkylcarboxylicacids are selected from the group of polyethylene glycol-150polyglyceryl-2 tristearate or PEG-150 diglyceryl tristearate or PEG-150tetraglyceryl distearate.
 13. The method as claimed in claim 1 or 2,characterized in that the concentration of the adhesion promoter in theagent is between 2% by weight and 60% by weight, preferably between 7and 50% by weight and particularly preferably between 8% by weight and40% by weight.
 14. The method as claimed in claim 1 or 2, characterizedin that the concentration of the adhesion promoter in the agent isbetween 15% by weight and 80% by weight, preferably between 20 and 70%by weight and particularly preferably between 30% by weight and 50% byweight.
 15. The method as claimed in claim 1 or 2, characterized in thatthe fillers further comprise thickeners, fragrances, dyes, salts, foamstabilizers, foam boosters, or foam generators.
 16. The method asclaimed in claim 1 or 2, characterized in that the surfactant fractionin the agent is between 10 to 60% by weight and preferably 25 to 45% byweight.
 17. The method as claimed in claim 1 or 2, characterized in thatthe surfactants are pulverulent or highly pasty.
 18. The method asclaimed in claim 1 or 2, characterized in that the surfactants areanionic surfactants and are selected from the group of salts ofcarboxylic acids, sulfuric acid half-esters, and sulfonic acids.
 19. Themethod as claimed in claim 1 or 2, characterized in that the surfactantsare nonionic surfactants and are selected from the group of alcoholethoxylates, alkyl glycosides, alkoxylated fatty acid alkyl esters,amine oxides and alkanolamides.
 20. The method as claimed in claim 15,characterized in that the agent comprises fragrances or perfume oils ina concentration between 0.25% by weight and 20% by weight, preferablybetween 3% by weight and 15% by weight and particularly preferablybetween 5% by weight and 10% by weight.
 21. The method as claimed inclaim 15, characterized in that the agent comprises up to 90% by weightof salts, in particular up to 10% by weight, preferably up to 5% byweight, of salts, preferably from the group of alkali metal and alkalineearth metal salts of strong acids or of mono-, di- and polycarboxylicacids.
 22. The method as claimed in claim 15, characterized in that theagent comprises thickeners from the group of bentonites, powdersurfactants, xanthans, polybutadiene rubbers, polyisopropenes, blockcopolymers, aryl ethoxylates or alkyl-aryl ethoxylates.
 23. The methodas claimed in claim 1 or 2, characterized in that the agent is awater-soluble and/or water-dispersible temporarily adhering adhesive.24. The method as claimed in claim 1 or 2, characterized in that theagent comprises cleaning and/or deodorization and/or bleaching and/orcoloring additives.
 25. The method as claimed in claim 1 or 2,characterized in that the agent is ointment-like, pasty and/orcream-like and dimensionally stable.
 26. The method as claimed in claim1 or 2, characterized in that the surface tension of the agent isbetween 50 and 65 mN/m, in particular below 60 mN/m.